Process of producing quaternary ammonium salts and products thereof



2,694,715 Patented Nov. 16, 1954 United States Patent Ofiice PRGEESS OF'PRODUCING QUATERNARY ANHVIO- NIUM SA'LTSANDPRODUCTSTHEREOF Richard D. Stayner, Albanyacalifi, assignor toz'California Research.- Corporation', San: Francisco," Calif., 21 corporation of Delaware No Drawing. Application December 20,1949, Serial, No. 134,139

6' Claims (Cl; 260-290) This invention relates to a new and useful process of producing quaternary ammonium;salts andto-novel quaternary ammonium salts prepared thereby.

More specifically, this invention relates-to the production of quaternary ammonium. salts-by' directlyhalogenating hydrophobic aliphatic group substituted aryl compounds which are; then. condensed with tertiary amines, saidlhydrophobic aliphatic. group substituted aryl compounds being characterized by an: aliphatic group having av carbon. atom with at leastxtwo hydrogens attached which isadjacent to another carbon atomtwhichdn turn is attached to a double bond.

Among. the novel and useful, quaternary ammonium salts which mayv be preparedaccording to the above. process, this invention concerns more particularly anewclass ofhalogenated alkyl aryl-methyl-quaternary ammonium salts having the general formula wherein R is an alkyl radicaloffrom 6' to 18- carbon atoms, Ar is an aromatichyd'rocarbon nucleus, X. is a .halogemn is from 1 to 8;.R is a methyLradicaI, mis from 0. to 4; R1, R2 and R3. are substituents of.-hydrocarbonstructure containing; a-maximum: of 12 carbon atoms,

Compounds. of the. above. formula. are prepared by directly halogenating-an alkyl aryl. compound. selected from "the group consisting of 'alk'yltoluene; alkylxylenes, alkyl trimethyl benzenes, .alkyltetramethyl benzenes' and alkyl'pentamethylbenzenes. 'The halogenatedalkyl aryl product-isthenreacted with atertiary amine toformthe quaternary ammonium .salt. according to the reaction.-

The halogenation is carried out in .the absence of catalysts The .-reaction between' theechlorinatedalkyl aromatic the chlorination of petroleumfractions.

and the tertiary amine may be carried out in the presence of a solvent if greater fluidity is desired for the reaction mixture. Methanol and isopropanol are desirable solvents for the preparation, alth'oughother solvents such as ethanol, dioxane, ethyl acetate; toluene and water are also applicable. I

The alkyl radical R maybe anyacyclic alkyl group'of from 6 to 18 carbon atoms withinthe broader aspects of the invention. In the ca'seo'f straight chain-acyclic'alkyl radicals those containing as fewas 6 to 10 carbon atoms are very satisfactory, but alkyl groupshaving from 1.0 to 18 carbon atoms are more s'atis'factory' when.branchedchain structures predominate. Particular sources of alkyl groups which are suitable forthe-invention' are the long-chain olefins of from 6 to118 carbon atoms; which may be obtainedfrom cracked-olefini c petroleum fractions or from Fischer-Tropsch synthesis. Although the preceding acyclic alkyl types of groups are operative,

the preferred alkyl group is that obtained from acyclic polypropylene havingfrom'9to l5 carbon'atoms. Polymers of this type are* the propylenetrirners, propylene tetramers, and propylene pentamers; For the purposes of this invention, propylene" polymers of from 12 to 15 carbon atoms produce a superior type of alkyl radical.

-Mixtures of propylene polymers boiling within the range from aboutQOO" F. to about 600 F; when utilized as a source of thealkyl radical give a chain" of from 9 to 18 carbon atoms in length. A propylen'e polymer mixture boiling from about 360? to about 520 F. provides alkyl radicals of from 12"to'15 carb'on'atoms' in length.

It isnot necessary that pure' long chain' aliphatic compounds be used to provide the 'alkyl groupsflof from 6 to 18carbon atoms. Ot her'sourceso'flong chain hydrocarbon mixtures aremixtirtes of. alcohols derived from catalytic hydrogenation ofi'th'e fatty acids contained in various glyc'erides; such as =coconuti0il; etc; These alcohols may'be'use'd 'directly to provide the'alkyl group or may be dehydrated to form a mixture of olefines: suitable for the" invention; although somewhat costlier: than the more desirable petroleumsources.

Additional petroleum sources of acyclic alkyl groups Within the scope of this'in'ven'ti'onarethoseobtained via These chlorinate'd hydrocarbon mixtures may then be" condensed with an aromatic hydrocarbon nucleus} to"'produce suitable alkyl aryl compounds; ;An eXample"ofthis type is'the chlorinated kerosene distillate productive of keryl aromatics' contemplated in this" invention, In addition to the propylene polymers; other synthetic petroleum" fractions of ahighl'y-'branched aliphatic nature falling, within the range offrom 10' to 18 carbon atom's'are also useful a'sa source for desirable} alkylradicals. Those products obtained in themanufacture of iso-octane by the alkylation' of isobutanewith isobutene orbutene are further examples'of this type, but inot as preferred as the 'polypropylenes' of from 9to 15 carbon'atoms.

The preceding types of alkyl radicals -are illustrative of those'characterizing the above described novel quaternary ammonium salts Thetgeneral process according to this invention is applicable to ar-yl compounds having other more Widely varying radicals; This process only requires that-oneof'the aliphatic groups of thehydrophobic aliphaticaryl"compoundspossess a carbon atom withxat least twohydrogens attachedvwhich 'is adjacent to anotherrcarbon atom which, in-turn ,=iis attached toa-double bond. The "double bond can rbe'zcontaine'diin an aromatic nucleusa It-can also be situated onuthealiphatic radical. Radicals of this latter typefare illustrated by theformulae etc., wherein R is aliphatic and contains a total of from 1 to 18 carbon atoms. Aliphatic groups of this kind can be derived from both natural and synthetic sources. For example, either thionic or carboxylic acids and their derivatives produce radicals of these types.

The aromatic hydrocarbon nucleus of the novel quaternary ammonium salts prepared according to the process of this invention can be benzene, naphthalene, anthracene, etc. However, a benzene nucleus 1 s preferred for present purposes. When the solubility of the quaternary ammonium compound in either water or oil is critical, those aromatic hydrocarbon nuclei containing 6 to 10 atoms are desirable.

The tertiary amines that are used according to thls invention can be either cyclic or aliphatic. They should possess a maximum of 12 carbon atoms and preferably from 3 to 10 carbon atoms. Of the cyclic radicals, both cyclic substituted or heterocyclic amines are suitable for this invention. Examples of these types are pyridine, unreduced nitrogen bases from petroleum, N-alkyl substituted reduced nitrogen bases from pctroleum, N-methyl piperidine, N-methyl morphollnet, lutidine, and others. Suitable mixed alkyl aryl tertiary amines, for example, are dimethyl benzyl amine, diethyl benzyl amine, methyl ethyl benzyl amine, etc. Illustrative of the tri-alkyl tertiary amines suitable for this invention are trimethyl amine, triethylamine, dimethyl ethyl amine, diethyl methyl amine, and amyl dimethyl amine. All of the preceding tertiary amines are either known to the art or can be prepared by conventional processes.

The halogenation step in the process according to this invention can be carried out by any of the means known to the art. As already mentioned, the reaction is preferably in the absence of iron salts and other similar chlorination catalysts which cause the chlorine to go onto the aromatic nucleus rather than the aliphatic radical. The halogenation can be performed with bromine, or chlorine. Sulfuryl chloride used in the presence of actinic light or with organic peroxides as, for example, benzoyl peroxide is another suitable halogenation agent. However, for the preferred process of this invention, chlorine has been found to be more satisfactory because of its reactivity and general availability.

The halogenation can be performed under many conditions that are known to the art. It can be carried out in the dark, in diffused light, or in the presence of actinic light to obtain successful results. Various temperatures customarily utilized in halogenation operations can be applied to the process of this invention.

In the case of chlorination with sulfuryl chloride, the

reaction temperature can be maintained in a suitable solvent by heating the mixture to the reflux temperature of the solvent. Examples of such solvents are benzene, carbon tetrachloride, etc. The chlorination with chlorine generally can be effected over a broad 80 C. to about 100 C. The halogenation can be carried out to any desired degree. However, in the case of chlorination it is desirable to add from about 1 to about 8 moles of chlorine per mole of alkyl aryl compound. The amount of chlorine depends on the alkyl aromatic. For example, in the case of alkyl toluenes about 6.5 moles of chlorine per mole of alkyl toluene is preferred. In the case of alkyl aryl compounds containing a higher number of ring methyl groups smaller amounts of chlorine, less than 6.5, are preferred.

The quaternary ammonium salts prepared according to the invention can be used in either the crude state in which they are obtained by the above described reactions or they may be purified to separate the unreacted materials from the salts using methods known to the art. Products derived from the more highly methylated alkyl aryl compounds which are treated with smaller amounts of halogen are desirably purified. They OIdlnarily contain a larger proportion of unreacted alkyl aryl compounds than those derived from the more heavily chlorinated alkyl aryl compounds have fewer methyl groups such as the alkyl toluenes and alkyl xylenes.

The purification can be accomplished by separating the quaternary salts and unreacted alkyl aryl compounds in accordance with any suitable method known to the art. One procedure is to dissolve the crude reaction product in water-alcohol solvent and then extract the non-quaternary oily materials containing chlorinated alkyl aromatics, etc., with a substance such as petroleum ether. The purified quaternary salt is obtained by evaporating the extracted water-alcohol solvent mixture. The non-quaternary oily materials are recovered by evaporating the ether extract portion and may then be recycled.

The following examples serve to illustrate this mvention but are not to be considered in limitation thereof.

Example I.Preparation of chlorinated dodecyl-benzyl pyridinium chloride.

A solution of 78 parts of 2-tolyldodecane, 8 1"parts of sulfuryl chloride, 0.25 part of benzoyl peroxide and 75 parts of benzene was refluxed for 2 hours. The solvent was then removed under reduced pressure to give 100 parts of chlorinated 2-tolyldodecane which contained 17.6 per cent chlorine.

A solution of 95 parts of the chlorinated 2-tolyldodecane, 20 parts of pyridine and parts of toluene was refluxed for 6 hours and cooled. The reaction mixture was diluted with petroleum ether to prepicipate the tc luaternary ammonium salt which was then separate The chlorinated dodecylbenzyl pyridinium chloride was dissolved in water to produce clear solutions which foamed readily. The material possessed a phenol coefficient of 170 against E. typhosa and 170 against S. aureus.

Example 2.-Preparation of chlorinated dodecyl-mxylyldimethylbenzylammonium chloride.

410 parts of dodecyl-m-xylene (from C12-C15 fraction of polypropylene) was warmed to 80 C. and then 400 parts of chlorine was passed into the stirred liquid. About 200 parts of product was obtained and corresponded to a tetrachloro derivative. The per cent chlorine was found to be 35.1%.

parts of the chlorinated dodecyl-m-xylene was mixed with 50 parts of ethanol and 10 parts of dimethylbenzylamine. The mixture was refluxed for 30 minutes, cooled, diluted with water and extracted with 3-50 ml. portions of petroleum ether. The chlorinated dodecyl-m-xylyldimethylbenzyl ammonium chloride solution was evaporated to near dryness and dissolved in sufficient 20 per cent alcohol to make a 10 per cent solution.

The above material possessed a phenol coeflicient of 130 against E. typhosa and 147 against S. aureus.

Example 3.--Preparation of chlorinated dodecylbenzyl trimethyl ammonium chloride.

277 parts of dodecyl toluene was treated with chlorine at l00 C. until the increase in weight was 234 parts. The chlorinated dodecyl toluene was blown with an inert gas to remove the last traces of hydrogen chloride. The per cent chlorine was found to be 45.15% which corresponds to 6.6 atoms of chlorine per mol.

506 parts of the chlorinated dodecyl toluene was mixed with 100 parts of methanol and warmed to 50 C. While stirring, 60 parts of trimethylamine gas was passed into the mixture, the tempreature being maintained at 50-60 C. When the addition was complete the mixture was stirred at 60 C. for 30 minutes and cooled. The crude product contained 80 per cent solids.

The chlorinated dodecylbenzyl trimethyl ammonium chloride thus obtained gave clear solutions up to 50 per cent in water. It possessed a phenol coeflicient of against E. typhosa and 94 against S. aureus.

The proportions in the preceding examples are taken on a weight basis. The efiicacy of various quaternaries prepared from chlorinated alkyl aromaticsin accordance with the process of this invention as described above is illustrated by the tests given in the following table.

spasms TABLE Evaluation of qnatemarzes from chlorinated alkylaromatics as germzczdes 'Oh1o-.- j Bacteria-a. Bacteriorine i? Purifl- 582? fi? 355? static mm 353*? N 0. Alkyl Group Aromatic Atoms Tertiary Amine Activity Activity per Ch1ocation T. rosa- E. ty- S. S mew A Gem Activity M01 rmatlnn crum phosa aureus a Dim (p. p. m.)

. See. dodecyl. 3 A N P 013-015 P. P 2 A (CH3)3N P 9-0 2 P. P..- 2 A (CH3)3N P 9-012 P. P; 2 I A (OEZDaN P (recycle); r09 P. P 3 A (CHQQN P 012-0151 d 3 A (CHa)sN C 0 2-015 Mixed m-p- 0.75 A (CH3)3N P xylene. 012015 P P... Toluene- 2 B (CH3)3N P d 4 B (CHs)aN P 6.7 B (CHs)aN P S. B CHMN P 2 I B (CH3)3N P 4' B (CHzds'N P 6 B (CHihN P 8 B (GHa'iaN P 4 B (CHahWCHzPh P 3.5 B, (CH3)3N C 5. 0. g B'." (CH3)3N c 3. B" (CH3):N C 3. 5 B (OHs)aN C 6;6 B .(GHal'aN C 15.5 B (CHmN C V 6.5 B (CH3')3N D 6.5 B (CHa):sN E; 5.0 B (CHC'QKN D Cur-C P. Pa." 5.0 B (CH3)3N F P. P.=propylene polymer.

A:refluxed with sulfuryl chloride and a trace of benzoyl peroxide in benzene.

Bzchlorine.

B*:used a tungsten filament lamp (actinic light)j on the reaction mixture during the chlorination.

Pzpurified by extracting a water-alcohol solution of the product with petroleum ether followed by evaporation of the water-alcohol solution.

The results set forth in the preceding table were obtained by testing the products prepared according to this invention both as to their phenol coetficients and bacterio-static and algae-static values. The phenol coelfi cient illustrates the killing power of the quaternary ammonium salts, While the bacterio-static and algae-static values signify the maximum dilution which can be obtained and still prevent the growth of bacteria and algae. The methods of testing utilized in obtaining the phenol coefiicients in results of the above table are outlined in the U. S. Food and Drug Administration method of testing antiseptics and disinfectants contained in U. S. Department of Agriculture Circular No. 198, December 1931. The evaluations were carried out at C. and Letheen broth was used in the subculture to prevent bacteriostasis.

It will be noted from the above table that the quaternary ammonium salts of this invention are effective in both water and oil solutions. For example, in tests 23 and 25, the material is shown to possess high germicidal and basterio-static qualities in the form of a water solution. In tests 24 and 26 its elfectiveness in oil solutions is illustrated. In regard to test 24, wherein the crude quaternary ammonium salt was worked up as a 10% pine oil solution, it was found to possess antiseptic properties of an altogether unexpectedly high degree. For example, pine oil, when evaluated alone, was found to have a phenol coeflicient of about 4 to 5. On the other hand, the quaternary ammonium salt by itself would have a coeflicient of about 85 (as shown by item 21 in the table). Yet when the two were combined the net result exceeded all expectations. The 10% pine oil solution possessed a phenol coeflicient of 20 which indicates a phenol coefiicient of 160 for the chlorinated quaternary ammonium salt on a 100% basis. Thus, it may be seen that the effectiveness of an antiseptic oil solution of the quaternary ammonium salts of this invention is so much more than merely cumulative of the individual antiseptic properties of the components as to be entirely unpredictable.

By referring to column 7 of the above table, it will be noted that the tests were performed on both purified and crude quaternary ammonium salts of this invention.

C'zcrude-reaction product worked. up in isopropanol without purlfication. :crudoreaction product 'workedrupns a Water solution, Eicrude reactionsproduct worked-11p as a 10% pine oil soluion. F' crude reaction product-worked up 39-20% in pineoil (60%) pineoiL, (20%) Water:and;(20%-) active'salt. Allv evaluations based upon'-tl1e. active :basis.

In, the-,caseof'. the purified, salts, the reaction'product from the condensation with tertiary amines was dissolved in water-alcohol solvent and extracted with petroleum ether to remove oil constituents comprising the chlorin ated alkyl aromatics. The Water-alcohol solvent containing the salt was then evaporated to produce the purified product. The petroleum ether can be evaporated from the oil portion to obtain the uncondensed chlorinated alkyl aromatics, which may then be recycled to the chlorination phase of the process. The example of item 4 in the table illustrates a preparation using the recycling step.

It will be noted from the table, however, that the products are quite efiective in their crude state. In experiments with the crude products it has been found that the degree of chlorination of the alkyl aromatics is a factor afiecting the physical properties of the salt. For example, if about 5 mols of chlorine per mol of the alkyl toluene are used, 10% solutions of the product in water are slightly turbid, indicating that not all of the alkyl aryl compound is converted to the chloro-alkylbenzyl chloride and the corresponding quaternary salt. On the other hand, if 6.0 mols of chlorine are used, the aqueous solutions are clear at all concentrations up to at least 50% concentration.

The chlorinated quaternary ammonium salts of this invention possess many remarkable properties, indicating a great number of possible applications. They show marked interfacial tension depressions in mineral oilwater mixtures, and possess excellent emulsifying properties. Their surface-active properties indicate that the compounds of this invention may be used as ore-flotation agents, dispersants for oil Well drilling mud, asphalt antistripping agents, bactericides and bacterio-static agents, fungicides and fungistatic agents, algaecides and algaestatic agents and mildew-proofing agents, as well as many other applications.

In view of the foregoing disclosure, variations and modifications of the invention will be obvious to those skilled in the art. All such variations and modifications as come within the scope of the appended claims are contemplated within this invention.

I claim:

1. A chlorinated quaternary ammonium salt having the formula:

CHr N Cl R wherein R is a dodecyl radical, and n is from 1 to 8.

2. A chlorinated quaternary ammonium salt having the formula:

OH: CHr-N CH: Cl R CH:

wherein R is a dodecyl radical and n is from 1 to 8.

4. A process which comprises passing chlorine into dodecyl toluene in the ratio of from about 1 to about 8 mols of chlorine per mol of dodecyl toluene at a temperature of 30-150 C. and thereafter condensing the ch10- rinated dodecyl toluene with one mole of trimethyl amine.

5. A process for preparing chlorinated alkyl benzyl quaternary ammonium salts which comprises passing 1 to 8 moles of chlorine into 1 mole of alkyl benzene hydrocarbon having 1 alkyl radical of from 6 to 18 carbon atoms and at least 1 methyl group attached to the benzene ring at a temperature of 30 to 150 C. and reacting the chlorinated alkyl methyl benzene thus obtained with 1 mole of a tertiary amine selected from the group consisting of pyridine, N-methyl piperidine, N-methyl morpholine and N,N-dialkyl-N-benzy1 and trialkyl amines of not more than 12 carbon atoms.

6. A chlorinated quaternary ammonium salt having the formula wherein R is an alkyl radical of from 12 to 15 carbon atoms and n is from 1 to 8, and the radical corresponds in structure to a tertiary amine selected from the group consisting of pyridine, N-methyl piperidine, N-methyl morpholine and N,N-dialkyl-N-benzyl and trialkyl amines of not more than 12 carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,314,111 Tucker et al Mar. 16, 1943 2,398,295 Epstein et al Apr. 9, 1946 2,416,264 McMullen et al Feb. 18, 1947 2,569,408 De Benneville et al Sept. 25, 1951 2,569,803 De Benneville et a1 Oct. 2, 1951 FOREIGN PATENTS Number Country Date 666,892 Great Britain Feb. 20, 1952 OTHER REFERENCES Wakelin: Manufacturing Chemist, vol. 10 (1939), page 17. 

5. A PROCESS FOR PREPARING CHLORINATED ALKYL BENZYL QUATERNARY AMMONIUM SALTS WHICH COMPRISES PASSING 1 TO 8 MOLES OF CHLORINE INTO 1 MOLE OF ALKYL BENZENE HYDROCARBON HAVING 1 ALKYL RADICAL OF FROM 6 TO 8 CARBON ATOMS AND AT LEAST 1 METHYL GROUP ATTACHED TO THE BENZENE RING AT A TEMPERATURE OF 30 TO 150* C. AND REACTING THE CHLORINATED ALKYL METHYL BENZENE THUS OBTAINED WITH 1 MOLE OF A TERTIARY AMINE SELECTED FROM THE GROUP CONSISTING OF PYRIDINE, N-METHYL PIPERIDINE, N-METHYL MORPHOLINE AND N,N-DIALKYL-N-BENZYL AND TRIALKYL AMINES OF NOT MORE THAN 12 CARBON ATOMS.
 6. A CHLORINATED QUATERNARY AMMONIUM SALT HAVING THE FORMULA 